EP0050375B1 - Hochabsorbierendes Harz - Google Patents

Hochabsorbierendes Harz Download PDF

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Publication number
EP0050375B1
EP0050375B1 EP81108744A EP81108744A EP0050375B1 EP 0050375 B1 EP0050375 B1 EP 0050375B1 EP 81108744 A EP81108744 A EP 81108744A EP 81108744 A EP81108744 A EP 81108744A EP 0050375 B1 EP0050375 B1 EP 0050375B1
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EP
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Prior art keywords
highly absorbent
absorbent resin
weight
water
neutralization
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Expired
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EP81108744A
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English (en)
French (fr)
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EP0050375A1 (de
Inventor
Hirotoshi Miyazaki
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Kuraray Co Ltd
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Kuraray Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C09K17/42—Inorganic compounds mixed with organic active ingredients, e.g. accelerators
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • A61L9/048—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating air treating gels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/12—Materials for stopping leaks, e.g. in radiators, in tanks

Definitions

  • This invention relates to a highly absorbent resin which is essentially a polyamine-crosslinked, partial neutralization product obtained by reaction of an alkali metal hydroxide with a carboxyl-containing polymer selected from the group consisting of alpha-olefin-maleic anhdyride copolymers and copolymers of a vinyl compound selected from the group of styrene, vinyl chloride, vinyl acetate, vinyl propionate, methyl vinyl ether and acrylonitrile with maleic anhydride, said resin being capable of absorbing at least 20 times its own weight of distilled water and having good durability and good heat resistance in the hydrous condition.
  • a carboxyl-containing polymer selected from the group consisting of alpha-olefin-maleic anhdyride copolymers and copolymers of a vinyl compound selected from the group of styrene, vinyl chloride, vinyl acetate, vinyl propionate, methyl vinyl ether and acrylonitrile with maleic anhydride
  • materials capable of absorbing at most 10 and odd times their own weight of water including synthetic resins useful as ion exchangers or ion adsorbers (see, for example, Japanese Patent Application Kokai No. 50-78,583), fibrous materials (e.g. absorbent cotton, wool), pulp, and porous particulate or granular inorganic materials (e.g. porous active carbon, vermiculite), hydrophilic polymeric materials capable of absorbing at least 20 times their own weight of distilled water have recently become subjects of increasing interest because of their high water-absorbing capacity.
  • synthetic resins useful as ion exchangers or ion adsorbers see, for example, Japanese Patent Application Kokai No. 50-78,583
  • fibrous materials e.g. absorbent cotton, wool
  • pulp e.g. absorbent cotton, wool
  • porous particulate or granular inorganic materials e.g. porous active carbon, vermiculite
  • those polymer materials that can, on contact with water, absorb a very large amount of water rapidly in a short time are expected to be useful in making sanitary napkins or tampons, diapers, disposable towels for kitchen use, and soil conditioners, for instance.
  • polymer materials there have recently been proposed several materials derived from natural or synthetic high molecular substances, such as crosslinked polyoxyethylene oxide, crosslinked polyvinyl alcohol, hydrolyzates of starch- or cellulose-polyacrylonitrile graft copolymers and crosslinked carboxymethylcellulose.
  • the requirements to be met by the highly absorbent resin are that the physical properties of the resins in the hydrous condition, that is the physical properties of the hydrous gels, do not alter upon standing for a long period of time in the hydrous condition, that the resins can endure hot water for a long period, that the resins have good heat resistance, and that the resins are resistant to acids and alkalis.
  • the Highly absorbent resins derived from starch or carboxymethylcellulose when left standing in the hydrous condition, easily undergo biodegradation or decay and as a result they lack a sufficient degree of durability.
  • the highly absorbent resins derived from synthetic high molecular substances such as those consisting of copolymers of a hydrophilic vinyl monomer (e.g. acrylic acid, methacrylic acid) and diacrylate or dimethacrylate of a polyol (e.g. ethylene glycol) (Japanese Patent Application Kokai No. 55-99,986) and those consisting of urea resin- or melamine resin-crosslinked alpha-olefinmaleic anhydride copolymers (Japanese Patent Application Kokai No. 54-94,525), mostly contain ester or amide bond-containing crosslinks, and consequently are susceptible to hydrolysis in the hydrous condition or in the hot hydrous condition.
  • a hydrophilic vinyl monomer e.g. acrylic acid, methacrylic acid
  • a polyol e.g. ethylene glycol
  • Japanese Patent Application Kokai No. 54-94,525 Japanese Patent Application Kokai No. 54-94,525
  • the hydrolysis leads to breakage of the crosslinks, and, in most cases, the initial properties of hydrous gels cannot be retained for a long period.
  • the highly absorbent resins disclosed by Japanese Patent Application Kokai No. 53-25,666 or U.S. Patent No. 4,155,957 which are prepared by dissolving a lower olefin-maleic anhydride copolymer in ammonia water, adding thereto a compound containing at least two hydroxyl groups (e.g. ethylene glycol, propylene glycol, glycerol), a compound containing at least two amino groups (e.g. ethylenediamine, propylenediamine), a compound containing at least two epoxy groups (e.g.
  • diglycidyl ether or the like (e.g. glycidyl alcohol), together with an aqueous ethylene-vinyl acetate copolymer emulsion, and allowing the crosslinking reaction to proceed, lose their water-absorbing capacity almost completely on exposure to elevated temperatures.
  • a primary object of the present invention is to provide highly absorbent resins capable of absorbing 20 to 800 times their own weight of water (distilled water) and at the same time having good durability. Another object is to provide a method of producing highly absorbent resins having a desired absorbency in a very simple manner.
  • highly absorbent resins means resins giving absorbency values (g/g) of at least 20, preferably 50 or more, and consequently sharply distinguishable from the previously mentioned synthetic resins, fibrous materials, pulp, and porous materials such as porous active carbon and porous inorganic particles, which give absorbency values of at most 10 and odd.
  • Absorbent materials giving absorbency values of less than 20 can absorb water only at slow rates but cannot be used in cases where a great water-absorbing capacity is required, for example, in the cases of sanitary articles, diapers, disposable kitchen towels, water leak stoppers and soil conditioners. If soluble in water, the absorbent resins cannot be adequate for the above-mentioned applications.
  • the resins should have a degree of crosslinking such that they swell without dissolving in water. In most cases, the maximum absorbency is about 800 g/g, which is quite sufficient. Preferably, resins having an absorbency of 50-500 are generally used.
  • the "absorbency' is herein defined, unless otherwise stated, as parts by weight of distilled water absorbed by the absorbent resin per part by weight of the resin before swelling, hence may be expressed on the g/g basis.
  • good durability is meant that the highly absorbent resin does not degenerate or degrade in the hydrous condition, i.e. in the form of hydrous gel, during a prolonged period of storage, can endure hot water for a long period, and can resist acids and alkalis.
  • Absorbent resins having good durability alone can adequately be used as water leak stoppers, dehydrating agents, etc. in the field of industry and as soil conditioners, dew formation inhibitors, etc. in the field of civil engineering and construction.
  • “Producing highly absorbent resins having an absorbency as desired in a very simple manner” means that the crosslinking reaction can be conducted very easily and safely using water, which, in most cases, requires little consideration of possible environmental pollution thereby or recovery thereof, as the solvent and that, since the absorbency of the highly absorbent resin correlates in a very simple manner with the amount of crosslinking agent used, highly absorbent resins with an absorbency as desired can be obtained easily, hence the industrial production process can be carried out and controlled very easily.
  • the above objects are realized by providing highly absorbent resins which essentially are polyamine-crosslinked, partial neutralization products obtained by reaction of an alkali metal hydroxide with a carboxyl-containing polymer selected from the group consisting of alpha-olefin-maleic anhydride copolymers and copolymers of a vinyl compound selected from the group of styrene, vinyl chloride, vinyl acetate, vinyl propionate, methyl vinyl ether and acrylonitrile with maleic anhydride, the degree of neutralization of the said neutralization products being 0.4 to 0.8 equivalent of total carboxyl groups of the said carboxyl-containing polymer, the amount of polyamine having the general formula H4NH-CH2CH2)rNH2 in which n is an integer of 1 to 110 as a crosslinking agent being not more than 2 parts by weight per 100 parts by weight of the neutralization products on the uncrosslinked basis, said resins being capable of absorbing at least 20 times their own weight of distilled water.
  • the neutralization product of carboxyl-containing polymer to be used in accordance with the invention is an alkali metal neutralization product obtained by reacting an alklai metal hydroxide with a maleic anhydride copolymer comprising an alpha-olefin or a specific vinyl compound and maleic anhydride.
  • a maleic anhydride copolymer comprising an alpha-olefin or a specific vinyl compound and maleic anhydride.
  • the highly absorbent resins obtainable by crosslinking alkali metal neutralization products of the above-mentioned specific carboxyl-containing polymers with polyamines are free from the drawbacks which are inherent in the highly absorbent resins derived from other polymers than the above-mentioned carboxyl-containing polymers or from ammonium or amine salts of carboxyl-containing polymers, and at the same time are very excellent in physical and chemical stability, hence in durability, because ion complexes between the carboxyl group and polyamine are involved in the crosslinks.
  • hydrous gels prepared by adding water to the highly absorbent resins of the invention neither reveal any signs of breakdown in the hydrous gel structure nor significant change in the absorbency after storage in hermetically sealed containers at room temperature for more than a year, or after heating at 70°C. for several months, or after boiling at 100°C for several days. They are resistant to biodegradation by decaying microbes.
  • the hydrous gels are not disintegrated even when heated in aqueous solutions of acids or alkalis. In this manner, the resins have semipermanent durability even in the hydrous condition. It goes without saying that the resins are excellent in durability in the dry condition.
  • alpha-olefin as used herein includes within the meaning thereof straight or branched chain unsaturated aliphatic hydrocarbons containing 2 to 12, preferably 2 to 8, carbon atoms, such as ethylene, propylene, butene-1, butene-2, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, diisobutylene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene and 2-methyl-4,4-dimethyl-1-pentene.
  • the so-called return or spent BB fraction or stream may also be used.
  • the monomers may be used either alone or in combination of two or more species.
  • alpha-olefins, especially isobutylene are the most adequate monomers for the purposes of the present invention.
  • the ratio of the alpha-olefin or vinyl compound to maleic anhydride in such a maleic anhydride copolymer is optional only if the reaction product (alkali metal neutralization product) from the resulting copolymer and an alkali metal hydroxide would be soluble in water.
  • ethylene, isobutylene, styrene or methyl vinyl ether are used in an amount of about 1 to 3 moles, in most cases about 1 mole, per mole of maleic anhydride.
  • maleic anhydride copolymers may be used either alone or in combination of two or more species. It is desired that they have a molecular weight such that the intrinsic viscosity s ⁇ jthereof as measured in dimethylformamide at 30°C is within the range of 0.1 to 8 (dl/g), preferably 0.2 to 5 (dllg). When the intrinsic viscosity is smaller than 0.1, the rate of crosslinking becomes very slow and resins with high absorbency can hardly be produced. On the other hand, when the intrinsic viscosity is higher than 8, the viscosity of the solution prepared from the resin becomes so high that workability or operability problems tend to arise in the production of highly absorbent resins.
  • isobutylene-maleic anhydride copolymer is the most preferred one, because the viscosity of a solution thereof is relatively low, which renders it possible to carry out the reaction at a relatively high concentration, and because it gives highly absorbent resins with very good durability.
  • carboxyl-containing polymers are converted to alkali metal neutralization products by reacting them with alkali metal hydroxide. This reaction is effected, for example, by adding a carboxyl-containing polymer to an aqueous solution of an alkali metal hydroxide.
  • the alkali metal hydroxide to be used herein includes among others sodium hydroxide, potassium hydroxide and lithium hydroxide. It reacts with the acid anhydride functions of the carboxyl-containing polymer to render the same water soluble or at least hydrophilic if not completely water soluble. While the use of an alkali metal hydroxide is essential, two or more alkali metal hydroxides may be used in combination. A small amount of ammonia may be used to promote dissolution of the said carboxyl-containing polymer in water or accelerate the crosslinking reaction between the carboxyl-containing polymer and the polyamine, as mentioned after. On the contrary, the use of ammonia or an amine alone will result not only in formation of highly absorbent resins having an odor of ammonia or amine but also in significant decrease in durability thereof, hence cannot achieve the expected results.
  • the degree of neutralization of the carboxyl-containing polymer with an alkali metal hydroxide is within the range of 0.4 to 0.8, preferably 0.5 to 0.8.
  • the degree of neutralization of the carboxyl-containing polymer is outside said range, the resulting resins, though highly capable of absorbing water, are very low in durability, especially in resistance to hot water, in the hydrous condition.
  • degree of neutralization is used herein to report the extent to which the carboxyl groups contained in the polymer are neutralized with the alkali metal hydroxide on the basis such that the degree of neutralization is equal to 1 when two moles of alkali metal hydroxide is reacted with one mole of maleic anhydride.
  • polyamines are specifically used as the crosslinking agents.
  • agents capable of crosslinking the carboxyl-containing polymers such as epoxy compounds, polyhydric alcohols and isocyanates, among others
  • the water-absorbing capacity of the highly absorbent resin products fluctuates from lot to lot, or the resin manufacture requires very high temperatures or special solvents, so that the control of the crosslinking reaction becomes very difficult, or in some cases where some crosslinking agents are used, highly absorbent resins having good durability, which are the subjects of the present invention, cannot be produced.
  • the use of polyamines makes it very easy and simple to carry out the reaction on the industrial scale using water as the solvent.
  • the absorbency of the resulting highly absorbent resins is substantially decided by an exponential function of the amount of the crosslinking agent (polyamine) used. Therefore, preliminary determination of two or three absorbency values in correlation with the corresponding known amounts of polyamine will render it very easy to produce highly absorbent resins with desired degree of absorbency. Such characteristic features can specifically be noted only with polyamines. Moreover, the highly absorbent resins produced by crosslinking with polyamines are, as mentioned above, very excellent in durability.
  • Such polyamines are water-soluble polyamines having a general formula shown by H4NH-CH2-CH2m-NH2, wherein n is an integer of 1 to 110, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and straight or branched polyethyleneimine.
  • n is an integer of 1 to 110, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and straight or branched polyethyleneimine.
  • the polyamines have a molecular weight of 60-5,000.
  • the amount of the polyamine to be used per 100 parts by weight of the alkali metal neutralization product of the carboxyl-containing polymer is generally within the range of more than 0.05 part by weight to less than 2 parts by weight, depending on the kind of said alkali metal neutralization product and/or the polyamine.
  • the amount is significantly smaller than 0.05 part by weight, not only the highly absorbent resin product, when swollen, presents only extremely low gel strength, that is poor durability, but also such problems as mutual adhesion of the highly absorbent resin particles or partial dissolution of the resin in water are encountered, although the absorbency of the highly absorbent resin is favorably increased.
  • the amount of polyamine is preferably within the range of 0.14 to 1.7 parts by weight. This range is preferably employed in producing highly absorbent resins by crosslinking sodium neutralization products of isobutylene-maleic anhydride copolymers with polyethyleneimine, since polyethyleneimine used in amounts within this range gives highly absorbent resins with absorbency values of 20-800 g/g.
  • the amount of polyethyleneimine to be used for obtaining generally preferred high absorbent resins with absorbency values of 50-500 is calculated at 0.2 to 0.9 part by weight. This range is thus preferred for polyethyleneimine.
  • a typical method of crosslinking an alkali metal neutralization product of a carboxyl-containing polymer with a polyamine comprises dissolving the alkali metal neutralization product in a solvent such as water or an alcohol, preferably water, adding to the solution an adequate amount of the polyamine to bring about the desired degree of absorbency in the final highly absorbent resin product, and stirring the mixture until a homogeneous solution is formed, followed by drying and heat treatment.
  • a solvent such as water or an alcohol, preferably water
  • adding to the solution an adequate amount of the polyamine to bring about the desired degree of absorbency in the final highly absorbent resin product and stirring the mixture until a homogeneous solution is formed, followed by drying and heat treatment.
  • the solution of the alkali metal neutralization product there may also be used the solution formed when the alkali metal hydroxide is reacted with the carboxyl-containing polymer, as it is, without any inconvenience. Fairly severe conditions are required for the above-mentioned crosslinking reaction.
  • the drying and crosslinking reaction can be carried out in one and the same step.
  • the thus-produced highly absorbent resins present characteristic features which the conventional highly absorbent resins could never attain. Thus, they show high absorbency and are capable of absorbing 20-800 times their own weight of distilled water at high rates of water absorption. They are also excellent in absorption capacity to salt solutions, urine and blood. They are durable not only in the dry condition but also in the hydrous condition and can retain their performance characteristics constantly over a prolonged period of time.
  • the form of the thus-produced highly absorbent resins is not critical:
  • the resins may be crushed or comminuted in a conventional manner to form powders thereof or may have the form of films, without causing any inconvenience.
  • paper, woven or nonwoven fabrics, or the like may be coated with the solution prior to effecting the polyamine crosslinking, followed by drying and crosslinking.
  • the products are absorbent articles in the form of paper, woven or nonwoven fabrics or the like containing the highly absorbent resins.
  • the highly absorbent resins of the present invention are useful in a variety of applications.
  • they when used in making disposable diapers, sanitary articles, gauze, disposable towels and the like, they give articles excellent in liquid absorbing capacity.
  • they When mixed with soil, they increase the water- holding capacity of the soil.
  • the materials When they are used in making materials for interior decoration, the materials have dew formation inhibiting properties.
  • they When they are impregnated with pesticides, fertilizers and perfumery substances, for instance, leaching or washing away of these substances can be inhibited.
  • a concentration of these aqueous mixtures may be achieved.
  • the highly absorbent resins of the present invention can also be used favorably in such industrial applications as sealants, packings and water leak stoppers, for instance.
  • a mixture of 100 weight parts of isobutylene-maleic anhydride copolymer (the intrinsic viscosity s ⁇ j as measured in dimethylformamide at 30°C being 1.01; the molar ratio of isobutylene to maleic anhydride in the copolymer being 1:1; ISOBAM O- 10, product of Kuraray Isoprene Chemical Co., Ltd.), 26 weight parts of sodium hydroxide and 374 weight parts of water was stirred with heating.
  • a homogeneous aqueous solution of acidic sodium salt of isobutylene-maleic anhydride copolymer was thus prepared.
  • the degree of neutralization of the neutralization product was 0.5.
  • the highly absorbent resin powder thus prepared was insoluble in water, swelled rapidly in water and absorbed 280 g/g of distilled water.
  • the swollen resin was transparent, and showed a sufficient gel strength, without mutual adhesion of the resin particies.
  • the resin powder absorbed 85 g/g of 0.5% sodium chloride solution and 60 g/g of Ringer solution. Durability tests were conducted for the highly absorbent resin by the following methods:
  • the container is hermetically sealed so as to prevent evaporation of water, the mixture is stored at room temperature (15-25°C) for a year, and the condition of the hydrous gel is observed.
  • the condition of the hydrous gel remains unchanged as compared with the initial one, the result is reported by the mark 0; when partial dissolution of the hydrous gel is observed, by the mark A; and when dissolution is complete and the state of hydrous gel is not noted any longer, by the mark x.
  • the highly absorbent resin is heated at 150°C for 8 hours. Thereafter, the absorbency (absorbing capacity) of the resin is measured for distilled water.
  • the highly absorbent resin is heated at 180°C for 8 hours. Thereafter, the absorbency of the resin is measured for distilled water.
  • the degree of neutralization of said neutralization product was 0.6 (0.5 based on potassium hydroxide, 0.1 based on ammonia, 0.6 in total).
  • the highly absorbent resins thus produced absorbed 360 and 140 g/g of distilled water, respectively. These resins were subjected to the durability tests described in Example 1, and the results as shown in Table 1 were obtained. As is evident therefrom, the highly absorbent resins were excellent in durability and heat resistance.
  • a highly absorbent resin containing potassium neutralization product of carboxyl groups and carboxy amide groups was prepared by graft copolymerizing acrylonitrile on starch, followed by hydrolysis with potassium hydroxide. The absorbency of this highly absorbent resin was 380 g/g. This highly absorbent resin was subjected to the durability tests as described in Example 1, and the results as shown in Table 1 were obtained.
  • a homogeneous aqueous solution was prepared by blending 100 weight parts of isobutylene-maleic anhydride copolymer as used in Example 1, 31 weight parts of sodium hydroxide and 369 weight parts of water. The degree of neutralization was 0.6. Polyethyleneimine having a molecular weight of 1,200 was added in various amounts as given in Table 2 to 500 weight parts of said aqueous solution. After sufficient stirring, each solution was poured into a square Teflon vat (70 x 70 cm). The film thus prepared was dried in air oven maintained at 120°C, then further heat-treated at 170°C for 3 hours, and crushed to give a highly absorbent resin powder having a particle size of 0,84 mm (corresponding to 20-mesh).
  • the thus-prepared highly absorbent resin was subjected to a test for absorbency for water (distilled water) and the durability tests as described in Example 1, and the results as shown in Table 2 were obtained.
  • Plotting the absorbency values against the amounts of polyethyleneimine on a logarithmic graph paper revealed a substantially straight line relationship therebetween.
  • the gradient and section are determined by the kind of the carboxyl-containing polymer used, the degree of neutralization thereof, the kind and amount of the polyamine used.
  • epoxy compounds, polyhydric alcohols, aminoalcohols or isocyanates are used as the crosslinking agents, such a relationship can never be found.
  • the relationship is specific to polyamines and makes it possible to obtain a highly absorbent resin with a desired absorbency directly.
  • a homogeneous aqueous solution of sodium neutralization product of styrene-maleic anhydride copolymer was prepared by mixing and heating 100 weight parts of styrene-maleic anhydride copolymer (the intrinsic viscosity [ ⁇ ] as measured in dimethylformamide at 30°C being 1.85; the molar ratio of styrene to maleic anhydride in the copolymer being 1:1; in Table 5, referred to as St-Man), 28 weight parts of sodium hydroxide and 372 weight parts of water.
  • the degree of neutralization of the neutralization product was 0.7.
  • To 500 weight parts of this aqueous solution was added 0.5 weight part of tetraethylenepentamine.
  • the thus-obtained highly absorbent resin (powder) was tested for absorbency with water (distilled water), 5% sodium chloride solution, 5% aqueous sodium hydroxide solution, Ringer solution and artificial urine, and also subjected to the heat resistance tests described in Example 1. The results of these tests were as shown in Table 5.
  • a highly absorbent resin was prepared by repeating the procedure of Example 6 using 53 weight parts of 25% aqueous ammonia and 347 weight parts of water instead of 28 weight parts of sodium hydroxide and 372 weight parts of water.
  • the highly absorbent resin obtained was subjected to the same tests as in Example 6, and the results as shown in Table 5 were obtained.

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  • Chemical & Material Sciences (AREA)
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Claims (5)

1. Hoch-absorbierendes Harz, welches im wesentlichen ein Polyamin-vernetztes partielles Neutralisationsprodukt ist, das durch Reaktion eines Alkalimetallhydroxids mit einem Carboxylgruppen enthaltenden Polymeren gebildet wurde, in dem der Neutralisationsgrad des Neutralisationsprodukts im Bereich von 0,4 bis 0.8 Äquivalent der Gesamt-Carboxylgruppen des Carboxylgruppen enthaltenden Polymeren liegt und die Menge des Vernetzungsmittels nicht mehr als 2 Gewichtsteile pro 100 Gewichtsteile des Neutralisationsprodukts, bezogen auf das unvernetzte Produkt, beträgt, wobei das Harz befähigt ist, mindestens das 20-fache seines eigenen Gewichts an destilliertem Wasser zu absorbieren und wobei das Carboxylgruppen enthaltende Polymere aus der Gruppe der a-Olefin-Maleinsäureanhydrid-Copolymeren und der Copolymeren einer Vinylverbindung aus der Gruppe Styrol, Vinylchlorid, Vinylacetat, Vinylpropionat, Methylvinylether und Acrylnitril mit Maleinsäureanhydrid ausgewählt ist und wobei das Vernetzungsmittel ein Polyethylenamin der allgemeinen Formel H―(NH―CH2―CH2)n―NH2 ist, in der n eine ganze Zahl von 1 bis 110 ist.
2. Hoch-absorbierendes Harz nach Anspruch 1, worin das a-Olefin Isobuylen ist.
3. Hoch-absorbierendes Harz nach Anspruch 1, worin die Vinylverbindung Styrol ist.
4. Hoch-absorbierendes Harz nach Anspruch 1, worin das Polyamin ein wasserlösliches Polyamin ist, das aus der aus Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin und Pentaethylenhexamin bestehenden Gruppe ausgewählt ist.
5. Hoch-absorbierendes Harz nach Anspruch 1, welches ein Polyethylenimin-vernetztes partielles Natrium-Neutralisations-produkt eines Isobutylen-Maleinsäureanhydrid-Copolymeren ist, wobei der Neutralisationsgrad des Neutralisationsprodukts 0,5 bis 0,8 Äquivalent der Gesamt-Carboxylgruppen des Copolymeren beträgt, die Menge an Polyethylenimin 0,14 bis 1,7 Gewichtsteile pro 100 Gewichtsteile des Neutralisations-produkts, bezogen auf das unvernetzte Produkt, beträgt und wobei das Harz befähigt ist, das 20- bis 800-fache seines eigenen Gewichts an destilliertem Wasser zu absorbieren.
EP81108744A 1980-10-22 1981-10-22 Hochabsorbierendes Harz Expired EP0050375B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP148639/80 1980-10-22
JP55148639A JPS6056724B2 (ja) 1980-10-22 1980-10-22 吸水性樹脂の製造方法

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EP0050375B1 true EP0050375B1 (de) 1985-08-14

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JPS5773007A (en) 1982-05-07
CA1162349A (en) 1984-02-14
US4389513A (en) 1983-06-21
EP0050375A1 (de) 1982-04-28
DE3171827D1 (en) 1985-09-19

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